A New Age of Innovation in Plastics Custom Polyolefins by Molecular - - PowerPoint PPT Presentation

Custom Polyolefins

JCS 12/02/2008 Page 1

Custom Polyolefins by Molecular Design:

A New Age of Innovation in Plastics

• Dr. Jim Stevens

Research Fellow The Dow Chemical Company

Custom Polyolefins

JCS 12/02/2008 Page 2

Consumer Durables and Appliances Electrical and Electronics Food and Specialty Packaging Health and Hygiene Industrial and Consumer Packaging Pipes and Fittings Rigid Packaging

Polyethylene is Everywhere

• Global demand exceeds 120 Billion pounds per year!
• Growing at ~5% per year, faster growth in emerging economies

Custom Polyolefins

JCS 12/02/2008 Page 3

• Polyolefins are often considered first to use in any application
• Excellent cost / performance value
• Ease of recycling
• Low energy to process and fabricate into films, parts, etc.
• State of the Business in 1990
• Industry-wide overcapacity and low profitability
• Producers discussing exit strategies such as mergers and outright

sales of assets

• Feeling that the big discoveries had already been made in

this area

• Feeling that the future belonged to those with low cost energy

and feedstocks

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JCS 12/02/2008 Page 4

Polymer Properties Determined by Catalysis

Lamella: long sequences of ethylene units fold into crystallites Tie molecule: Bridge more than one lamellar crystallite Interfacial regions: “defects” are excluded into amorphous regions

Composition and molecular structure of each polymer chain determined by relative kinetic rates:

catalyst

Catalysis Molecular Structure Bulk Structure Properties

Molecular structure of polymer chains determines bulk structure:

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JCS 12/02/2008 Page 5

The Evolution of Polyethylene:

LDPE

Radical mechanism (1933)

• High Temperature & Pressure
• Many reactions possible

Highly Branched:

• Excellent flow properties
• Fast extrusion rates
• Poor mechanical properties

An Evolution of Catalysis! LLDPE Coordination catalysis (1950’s)

• Low Temperature & Pressure
• Multiple catalytic sites
• Nobel Prize Ziegler & Natta 1963

Linear Backbone:

• Flexible and tough
• Chains are random lengths

mPE

“Single Site” catalysts (1990’s)

• Molecular catalysts
• Ability to design control into the

catalyst molecule

Homogeneous Polymers:

• Chains are similar lengths
• Complete control of branching

We now have the tools to control molecular structure (and properties) with exquisite precision!

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JCS 12/02/2008 Page 6

Two Important Discoveries in Basic Science Funded by DOE Office of Basic Energy Sciences

• Prof. John Bercaw – Caltech
• Poor catalyst but provided important

new information on catalyst structure

• Grant # DE-FG03-85 ER13431
• Published in Organometallics
• Prof. Tobin Marks – Northwestern
• New idea for activators for catalysts
• Grant # DE-FG02-86 ER13511
• Published in Journal of the American

Chemical Society

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JCS 12/02/2008 Page 7

Dow Chemical Constrained Geometry Catalyst

Constrained Geometry Catalyst (CGC)

From this To this

• Over 400 people involved in commercialization
• >2 billion pounds/yr plastics and elastomers

produced using INSITE catalyst

• Extremely efficient process for making

elastomers

• Less energy, less environmental impact, higher

utilization of resources

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JCS 12/02/2008 Page 8

Polyolefin Products Launched

AFFINITY* Polyolefin Plastomers 1993 ENGAGE* Polyolefin Elastomers 1994 ELITE* Enhanced Polyethylene 1996 NORDEL*IP EPDM (Solution Process EPDM) 1996 AFFINITY* Adhesives 1998 INDEX* Interpolymers 1999 Thermoplastic Polyolefins (TPO’s) 2000 INSPIRE* Performance Polymers 2000 Gas Phase Polyethylene (Sold to BP) 2001 Slurry Phase Polyethylene (Sold to Univation) 2001 DOW XLA* Elastic Fibers 2002 NORDEL* MG EPDM (Gas Phase EPDM) 2002 VERSIFY* Propylene Plastomers and Elastomers 2004 INFUSE* Olefin Block Copolymers 2007

Using New Catalysts

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JCS 12/02/2008 Page 9

Bio-Ethanol to Polyethylene

Polyolefins are now bio-polymers!

CO2

• 350 kT of LLDPE (700 MM lbs)
• 120,000 hectares of sugar cane in Brazil (450 square miles)
• Recyclable plastic (CO2 fixation)
• Cheaper than many fossil sources
• Lower capital footprint
• 8% of Dow LLDPE capacity
• Walled off from oil volatility

Custom Polyolefins

JCS 12/02/2008 Page 10

Manipulating Light with Self-Assembled Polyolefins

10 20 30 40 50 60 70 350 400 450 500 550 600 650 700 Wavelength, nm % Reflectance

Clear Glass White Plate Black Plate SampleA SampleA SampleA Transmitted Light thru clear glass plate Reflected light

• n solid black plate

Reflected light

• n solid white plate

Custom Polyolefins

JCS 12/02/2008 Page 11

Everyday Products Using INSITE* Technology

• Car bumpers, belts, window seals, and hoses
• Athletic shoes
• Crocs

‡ shoes

• “Plastic” wine corks
• Electrical wire jackets
• “Comfort-stretch” clothing
• Roofing membranes
• Food packaging

* Trademark of The Dow Chemical Company

‡ Trademark of Crocs, Inc.